Polyimide-based polymer film, substrate for display device, and optical device using the same

ABSTRACT

The present disclosure relates to a polyimide-based resin film which is synthesized by the reaction of an acid anhydride compound and a diamine compound having a specific structure, thereby capable of ensuring excellent flatness even under high temperature heat treatment conditions, and stably maintaining flatness even during further heat treatment, a substrate for display device, and an optical device using the same.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a 35 U.S.C. 371 National Phase Entry Application from PCT/KR2020/001250 filed on Jan. 28, 2020, designating the United States, which claims the benefit of priority from Korean Patent Application No. 10-2019-0013486 filed on Feb. 1, 2019; Korean Patent Application No. 10-2019-0121176 filed on Sep. 30, 2019; Korean Patent Application No. 10-2019-0121177 filed on Sep. 30, 2019; Korean Patent Application No. 10-2019-0121178 filed on Sep. 30, 2019; Korean Patent Application No. 10-2019-0161494 filed on Dec. 6, 2019; and Korean Patent Application No. 10-2019-0161495 filed on Dec. 6, 2019 in the Korean Intellectual Property Office, the disclosures of which are incorporated herein by reference in their entirety.

TECHNICAL FIELD

The present disclosure relates to a polyimide-based resin film capable of ensuring excellent flatness even under high temperature heat treatment conditions, and stably maintaining flatness even during further heat treatment, a substrate for display device and an optical device using the same.

BACKGROUND OF THE INVENTION

The display device market is rapidly changing based on flat panel displays (FPDs) that are easy to fabricate over a large area and can be reduced in thickness and weight. Such flat panel displays include liquid crystal displays (LCDs), organic light emitting displays (OLEDs), or electrophoretic devices.

In line with recent efforts to further extend the application and use of flat panel displays, particular attention has focused on so-called flexible display devices in which flexible substrates are applied to flat panel displays. The application of such flexible display devices is particularly reviewed based on mobile devices such as smart phones and the application fields thereof are gradually extended.

In general, in manufacturing a flexible display device and an illumination device, a TFT device is manufactured by forming a multilayer inorganic film such as a buffer layer, an active layer, and a gate insulator on the cured polyimide.

However, when light is emitted to the polyimide layer (substrate layer), the emission efficiency may be reduced due to the difference between the refractive index of the multilayer upper layer made of the inorganic film and the refractive index of the polyimide layer.

In addition, when the polyimide material included in the polyimide layer (substrate layer) is cured at a high temperature of 400° C. or more, optical properties may decrease due to deterioration of the polyimide.

Accordingly, there is a demand for developing a new polyimide that can satisfy high heat resistance and excellent optical properties.

BRIEF SUMMARY OF THE INVENTION

The present disclosure provides a polyimide-based resin film capable of ensuring excellent flatness even under high temperature heat treatment conditions, and stably maintaining flatness even during further heat treatment.

The present disclosure also provides a substrate for display device and an optical device using the same.

One aspect of the present disclosure provides a polyimide-based resin film comprising a polyimide-based resin containing a polyimide repeating unit represented by the following Chemical Formula 1, wherein Bow is 40 μm or less.

in Chemical Formula 1, X₁ is a tetravalent functional group represented by the following Chemical Formula 2, Y₁ is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted,

in Chemical Formula 2, Ar is a polycyclic aromatic divalent functional group.

Another aspect of the present disclosure provides a substrate for display device comprising the polyimide-based resin film.

A further aspect of the present disclosure provides an optical device comprising the polyimide-based resin film.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, a polyimide-based resin film according to specific embodiments of the present disclosure, a substrate for a display device and an optical device using the same will be described in more detail.

Unless otherwise specified throughout this specification, the technical terms used herein are only for reference to specific embodiments and is not intended to limit the present disclosure.

The singular forms “a”, “an”, and “the” used herein include plural references unless the context clearly dictates otherwise.

The term “including” or “comprising” used herein specifies a specific feature, region, integer, step, action, element and/or component, but does not exclude the presence or addition of a different specific feature, region, integer, step, action, element, component and/or group.

The terms including ordinal numbers such as “a first”, “a second”, etc. are used only for the purpose of distinguishing one component from another component, and are not limited by the ordinal numbers. For instance, a first component may be referred to as a second component, or similarly, the second component may be referred to as the first component, without departing from the scope of the present invention.

In the present specification, the (co)polymer means including both a polymer and a copolymer, the polymer means a homopolymer consisting of a single repeating unit, and the copolymer means a composite polymer containing two or more repeating units.

In the present specification, examples of the substituents are described below, but are not limited thereto.

In the present specification, the term “substituted” means that other functional groups instead of a hydrogen atom in the compound are bonded, and a position to be substituted is not limited as long as the position is a position at which the hydrogen atom is substituted, that is, a position at which the substituent can be substituted, and when two or more are substituted, the two or more substituents may be the same as or different from each other.

In the present specification, the term “substituted or unsubstituted” means being unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amide group; a primary amino group; a carboxy group; a sulfonic acid group; a sulfonamide group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkoxysilylalkyl group; an arylphosphine group; or a heterocyclic group containing at least one of N, O, and S atoms, or being unsubstituted or substituted with a substituent to which two or more substituents are linked among the substituents exemplified above. For example, “the substituent to which two or more substituents are linked” may be a biphenyl group. That is, the biphenyl group may also be an aryl group, and may be interpreted as a substituent to which two phenyl groups are linked.

In the present specification, the notation

or

means a bond linked to another substituent group, and a direct bond means the case where no other atoms exist in the parts represented as L.

In the present specification, aromatic is a property that satisfies Huckle's Rule, and a compound can be defined as aromatic if all of the following three conditions are satisfied according to Huckle's Rule.

1) There must be 4n+2 electrons that are completely conjugated by empty p-orbitals, unsaturated bonds, lone electron pairs, etc.

2) 4n+2 electrons have to form planar isomers and form a ring structure.

3) All atoms of the ring have to be able to participate in conjugation.

In the present specification, the alkyl group is a monovalent functional group derived from an alkane, and may be a straight-chain or a branched-chain. The number of carbon atoms of the straight chain alkyl group is not particularly limited, but is preferably 1 to 20. Also, the number of carbon atoms of the branched chain alkyl group is 3 to 20. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptane-4-yl and the like, but are not limited thereto. The alkyl group may be substituted or unsubstituted, and when substituted, examples of the substituent are the same as described above.

In the present specification, the haloalkyl group means a functional group in which the above-described alkyl group is substituted by a halogen group, and examples of halogen group are fluorine, chlorine, bromine or iodine. The haloalkyl group may be substituted or unsubstituted, and when substituted, examples of the substituent are the same as described above.

In the present specification, a multivalent functional group is a residue in which a plurality of hydrogen atoms bonded to an arbitrary compound are removed, and for example, it may be a divalent, functional group, a trivalent functional group, and a tetravalent functional group. As an example, a tetravalent functional group derived from a cyclobutane means a residue in which any four hydrogen atoms bonded to the cyclobutane are removed.

In the present specification, the electron-withdrawing group may include one or more selected from the group consisting of a haloalkyl group, a halogen group, a cyano group, a nitro group, a sulfonic acid group, a carbonyl group, and a sulfonyl group, and preferably, it may be a haloalkyl group such as trifluororumethyl group (—CF₃).

In the present specification, a direct bond or a single bond means being connected to a bond line in which no atoms or atomic groups exist at the corresponding position. Specifically, it means the case where no other atoms exist in the parts represented as L₁, or L₂ in Chemical Formula.

In the present specification, the weight average molecular weight means a weight average molecular weight in terms of polystyrene measured by GPC method. In the process of determining the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analyzing device, a detector such as a refractive index detector, and an analytical column can be used. Commonly applied conditions for temperature, solvent, and flow rate can be used. Specific examples of the measurement condition are as follows: Waters PL-GPC220 instrument with Polymer Laboratories PLgel MIX-B, 300 mm column was used, the evaluation temperature was 160° C., 1,2,4-trichlorobenzene was used as a solvent, the flow rate is 1 mL/min, samples were prepared at a concentration of 10 mg/10 mL and then fed in an amount of 200 μL, and the values of Mw could be determined using a calibration curve formed using a polystyrene standard. The molecular weight of the polystyrene standards used herein was 9 types of 2,000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000.

Hereinafter, the present disclosure will be described in more detail.

1. Polyimide Film

According to one embodiment of the present disclosure, there can be provided a polyimide-based resin film comprising a polyimide-based resin containing a polyimide repeating unit represented by Chemical Formula 1, wherein Bow is 40 μm or less.

The present inventors have found through experiments that as in the polyimide-based resin film of the one embodiment, a tetravalent functional group derived from tetracarboxylic dianhydride and a divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted, having a specific structure as shown in Chemical Formula 2, is contained within the polyimide-based repeating unit structure, and thereby, the polyimide resin film subjected to curing at a high temperature of 400° C. or more minimizes the occurrence of bow (warpage) and has high flatness, thereby completing the present disclosure.

In particular, since the polyimide-based resin includes a reaction product obtained through imidization reaction of a tetracarboxylic dianhydride containing a structure represented by Chemical Formula 2 and an aromatic diamine having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted, it is considered that high heat resistance is ensured by the physical and chemical action according to the novel structure of the acid anhydride monomer and the aromatic diamine monomer, so that excellent flatness is achieved not only in the cured film through heat treatment at a high temperature of 400° C. or more but also during additional heat treatment for the cured film at an elevated temperature of 400° C. or more.

Specifically, a polyimide-based resin synthesized from an aromatic diamine monomer having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted improves the ordering and orientation properties between molecules and ensure sufficient heat resistance even in the polyimide film obtained by high temperature curing, and when this is used as a plastic substrate, it can prevent the plastic substrate from being damaged by heat when heat treating the metal layer formed on the plastic substrate, and also can suppress the occurrence of bow of a metal thin film formed on the plastic substrate.

The polyimide-based resin is meant to include both a polyimide, and a precursor polymer thereof such as polyamic acid or polyamic acid ester. That is, the polyimide-based polymer may include one or more selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit. That is, the polyimide-based polymer may include one type of polyamic acid repeating unit, one type of polyamic acid ester repeating unit, one type of polyimide repeating unit, or a copolymer in which these two or more types of repeating units are mixed.

The one or more repeating units selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit may form a main chain of the polyimide-based polymer.

In particular, the polyimide-based resin may include a polyimide repeating unit represented by Chemical Formula 1.

In Chemical Formula 1, X₁ is a tetravalent functional group represented by Chemical Formula 2, the X₁ is a functional group derived from a tetracarboxylic dianhydride compound used in the synthesis of a polyimide-based resin.

In Chemical Formula 2, Ar is a polycyclic aromatic divalent functional group. The polycyclic aromatic divalent functional group is a divalent functional group derived from a polycyclic aromatic hydrocarbon compound or a derivative compound thereof, and may include a fluorenylene group. The derivative compound includes all compounds in which one or more substituents are introduced or a carbon atom is replaced with a heteroatom.

More specifically, in Ar of Chemical Formula 2, the polycyclic aromatic divalent functional group may include a fused cyclic divalent functional group containing at least two or more aromatic cyclic compounds. That is, the polycyclic aromatic divalent functional group may contain at least two or more aromatic ring compounds in the functional group structure, and also the functional group may have a fused ring structure.

The aromatic cyclic compound may include an arene compound containing one or more benzene rings, or a hetero arene compound in which carbon atoms in the arene compound are replaced with heteroatoms.

The aromatic cyclic compound may contain at least two or more in the polycyclic aromatic divalent functional group, and each of the two or more aromatic cyclic compounds may directly form a fused ring, or may form a fused ring via another ring structure. As an example, when two benzene rings are each fused to a cycloalkyl ring structure, it may be defined that two benzene rings form a fused ring via each cycloalkyl ring.

The fused cyclic divalent functional group containing at least two or more aromatic cyclic compounds is a divalent functional group derived from a fused cyclic compound or a derivative compound thereof containing at least two or more aromatic cyclic compounds, and the derivative compound includes all compounds in which one or more substituents are introduced or a carbon atom is replaced with a heteroatom.

Examples of the polycyclic aromatic divalent functional group are not particularly limited, but as an example, a fluorenylene group can be mentioned.

Examples of the tetravalent functional group represented by Chemical Formula 2 includes a functional group represented by the following Chemical Formula 2-1.

In Chemical Formula 1, Y₁ is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted, the Y₁ may be a functional group derived from a diamine compound used in the synthesis of polyamic acid, polyamic acid ester, or polyimide.

In the Y₁, the aromatic divalent functional group having 15 or more carbon atoms may include three or more aromatic cyclic compounds. As three or more aromatic cyclic compounds are contained in this way, the polyimide-based resin has improved ordering and orientation properties between molecules, and thus, it can ensure sufficient heat resistance even in a polyimide film obtained by high-temperature curing.

The aromatic divalent functional group having 15 or more carbon atoms may include one or more selected from the group consisting of a triphenylene group, a quarterphenylene group, and a pentaphenylene group.

The electron-withdrawing group may include one or more selected from the group consisting of a haloalkyl group, a halogen group, a cyano group, a nitro group, a sulfonic acid group, a carbonyl group, and a sulfonyl group.

As an electron-withdrawing substituent such as trifluororumethyl group (—CF₃) having high electronegativity are substituted, the effect of suppressing the formation of CTC (charge transfer complex) of Pi-electrons existing in the polyimide resin chain is increased, thereby ensuring improved transparency. That is, the packing in the polyimide structure or between the chains can be reduced, and due to steric hindrance and electrical effects, it is possible to weaken the electrical interaction between the chromophores and show high transparency in the visible region.

More specifically, the aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing functional group of the Y₁ is substituted may include a functional group represented by the following Chemical Formula 3.

in Chemical Formula 3, T₁ to T₃ are the same as or different from each other, and each independently, an electron-withdrawing group, m1 to m3 are the same as or different from each other, at least one of m1 to m3 is an integer of 1 to 4, the rest are an integer of 0 to 4, and n is an integer of 1 to 10.

The aromatic divalent functional group having 15 or more carbon atoms in which at least one electron withdrawing group of the Y₁ is substituted may include a functional group represented by the following Chemical Formula 3-1.

The polyimide-based resin may include a combination of a tetracarboxylic dianhydride represented by the following Chemical Formula 4 and an aromatic diamine having 15 or more carbon atoms in which at least one electron withdrawing group is substituted.

in Chemical Formula 4, Ar′ is a polycyclic aromatic divalent functional group. The polycyclic aromatic divalent functional group is a divalent functional group derived from a polycyclic aromatic hydrocarbon compound, and may include a divalent functional group derived from a fluorenylene group or derivative compound thereof, fluorenylene group. The derivative compound includes all compounds in which one or more substituents are introduced or a carbon atom is replaced with a heteroatom.

Specific examples of the tetracarboxylic dianhydride represented by Chemical Formula 4 include 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF).

The aromatic diamine having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted is a compound in which an amino group (—NH₂) is bonded to both terminals of the aromatic divalent functional group having 15 or more carbon atoms in which at least one of the above-mentioned electron-withdrawing groups is substituted. Details of the aromatic divalent functional group having 15 or more carbon atoms in which at least one of the above-mentioned electron-withdrawing groups is substituted are the same as described above.

Specific examples of the aromatic diamine having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted may include a diamine represented by the following Chemical Formula a.

More specifically, in the polyimide-based resin, a bond between the nitrogen atom of the amino group and the carbon atom of the anhydride group may be formed by a reaction between a terminal anhydride group (—OC—O—CO—) of the tetracarboxylic dianhydride represented by Chemical Formula 4, and a terminal amino group (—NH₂) of the aromatic diamine having 15 or more carbon atoms in which at least one of the electron withdrawing group is substituted.

The polyimide-based resin may further include a polyimide repeating unit represented by the following Chemical Formula 5.

in Chemical Formula 5, X₂ is one of the tetravalent functional groups represented by the following Chemical Formula 6, and Y₂ is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted,

in Chemical Formula 6, R₁ to R₆ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, L is any one selected from the group consisting of a single bond, —O—, —CO—, —COO—, —S—, —SO—, —SO₂—, —CR₇R₈—, —(CH₂)_(t)—, —O(CH₂)_(t)O—, —COO(CH₂)_(t)OCO—, —CONH—, phenylene or a combination thereof, where R₇ and R₈ are each independently one of hydrogen, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms, and t is an integer of 1 to 10.

Specific examples of the functional group represented by Chemical Formula 6 include a functional group represented by the following Chemical Formula 6-1, a functional group represented by the following Chemical Formula 6-2, or a functional group represented by the following Chemical Formula 6-3.

That is, the polyimide-based polymer may include a first repeating unit containing a repeating unit represented by Chemical Formula 1 wherein the repeating unit derived from tetracarboxylic dianhydride is a functional group represented by Chemical Formula 2; and a second repeating unit containing a repeating unit represented by Chemical Formula 5 wherein the repeating unit derived from tetracarboxylic dianhydride is a functional group represented by Chemical Formula 6. The first repeating unit and the second repeating unit can be randomly arranged in the polyimide-based polymer to form a random copolymer, or form a block copolymer by forming a block of the first repeating unit and a block of the second repeating unit.

The polyimide-based polymer including the repeating unit represented by Chemical Formula 1 and the repeating unit represented by Chemical Formula 5 can be prepared by reacting two or more different tetracarboxylic dianhydride compounds with a diamine compound, and the two types of tetracarboxylic dianhydrides can be added simultaneously to synthesize a random copolymer, or can be added sequentially to synthesize a block copolymer.

The polyimide repeating unit represented by Chemical Formula 5 may be contained in an amount of 1 mol % or more and 99 mol % or less with respect to the total repeating units contained in the polyimide-based resin.

The polyimide repeating unit represented by Chemical Formula 1 and the polyimide repeating unit represented by Chemical Formula 5 may be contained in an amount of 70 mol % or more, or 80 mol % or more, or 90 mol % or more, or 70 mol % or more and 100 mol % or less, 80 mol % or more and 100 mol % or less, 70 mol % or more and 90 mol % or less, 70 mol % or more and 99 mol % or less, 80 mol % or more and 99 mol % or less, 90 mol % or more and 99 mol % or less with respect to the total repeating units contained in the polyimide-based resin.

That is, the polyimide-based resin is composed of only the polyimide repeating unit represented by Chemical Formula 1 and the polyimide repeating unit represented by Chemical Formula 5, or most thereof can be composed of the polyimide repeating unit represented by Chemical Formula 1 and the polyimide repeating unit represented by Chemical Formula 5.

More specifically, the polyimide-based resin may not be mixed with other diamines in addition to diamines capable of inducing aromatic divalent functional groups having 15 or more carbon atoms in which at least one of the electron-withdrawing group is substituted, or may be mixed in an extremely small amount of less than 1 mol %.

More specifically, the polyimide repeating unit represented by Chemical Formula 5 may include one or more repeating units selected from the group consisting of a polyimide repeating unit represented by the following Chemical Formula 5-1, a polyimide repeating unit represented by the following Chemical Formula 5-2, and a polyimide repeating unit represented by the following Chemical Formula 5-3.

in Chemical Formula 5-1, X₃ is a tetravalent functional group represented by Chemical Formula 6-1, and Y₃ is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted,

in Chemical Formula 5-2, X₄ is a tetravalent functional group represented by Chemical Formula 6-2, and Y₄ is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted,

in Chemical Formula 5-3, X₅ is a tetravalent functional group represented by Chemical Formula 6-3, and Y₅ is an aromatic divalent functional group having 15 or more carbon atoms in which at least one electron-withdrawing group is substituted.

The weight average molecular weight (measured by GPC) of the polyimide-based resin is not particularly limited, but may be, for example, 1000 g/mol or more and 200000 g/mol or less, or 10000 g/mol or more and 200000 g/mol or less.

Because the polyimide-based resin according to the present disclosure can exhibit excellent colorless and transparent properties while maintaining properties such as heat resistance and mechanical strength as they are due to a rigid structure, it can be used in a diverse range of fields such as device substrate, display cover substrate, optical film, integrated circuit (IC) package, adhesive film, multilayer FRC (flexible printed circuit), tape, touch panel, protective polymer film for optical disc, etc. In particular, it can be suitable for display cover substrate.

Meanwhile, the polyimide-based resin film of the one embodiment may include a cured product in which the polyimide-based resin is cured at a temperature of 400° C. or more. The cured product means a material obtained through a curing step of the resin composition containing the polyimide-based resin, and the curing process may be performed at a temperature of 400° C. or more, or 400° C. or more and 500° C. or less.

More specifically, examples of the method of synthesizing the polyimide-based resin film are not particularly limited, and, for example, a method of manufacturing a film including a step of coating a resin composition containing the polyimide-based resin onto a substrate to form a coating film (step 1); a step of drying the coating film (step 2); and a step of heat-treating and curing the dried coating film (step 3) can be used.

Step 1 is a step of coating the resin composition containing the above-mentioned polyimide-based resin onto a substrate to form a coating film. The method of coating the resin composition containing the polyimide-based resin onto a substrate is not particularly limited, and for example, a method such as screen printing, offset printing, flexographic printing, inkjet, and the like can be used.

Further, the resin composition containing the polyimide-based resin may be in the form dissolved or dispersed in an organic solvent. In the case of having such form, for example, when the polyimide-based resin is synthesized in the organic solvent, the solution may be the reaction solution thus obtained itself or a solution obtained by diluting the reaction solution with another solvent. Further, when the polyimide-based resin is obtained as powder, the solution may be a solution obtained by dissolving the powder in an organic solvent.

Specific examples of the organic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate and the like. They can be used alone or in combination of two or more.

The resin composition containing the polyimide-based resin may include the solid in such an amount that the solution has an appropriate viscosity in consideration of processability such as a coating property during the film forming process. For example, the content of the composition may be adjusted so that the total content of the resin is 5% by weight or more and 25% by weight or less, or may be adjusted to 5% by weight or more and 20% by weight or less, or 5% by weight or more and 15% by weight or less.

In addition, the resin composition containing the polyimide-based resin may further include other components in addition to the organic solvent. In a non-limiting example, when the resin composition containing the polyimide-based resin is coated, additives capable of improving the uniformity of the film thickness and the surface smoothness, or improving the adhesion with a substrate, or changing the dielectric constant and conductivity, or increasing the denseness, may be further included. Examples of these additives include surfactants, silane-based compounds, dielectrics or crosslinking compounds, etc.

Step 2 is a step of drying the coating film formed by coating a resin composition containing the polyimide-based resin onto a substrate.

The step of drying the coating film may be performed by a heating means such as a hot plate, a hot-air circulation furnace, an infrared furnace and the like, and the drying may be performed at a temperature of 50° C. or more and 150° C. or less, or 50° C. or more and 100° C. or less.

Step 3 is a step of heat-treating and curing the dried coating film. In this case, the heat treatment may be performed by a heating means such as a hot plate, a hot-air circulation furnace, an infrared furnace and the like, and the heat treatment can be performed at a temperature of 400° C. or more, or 400° C. or more and 500° C. or less.

The thickness of the polyimide-based resin film is not particularly limited, but for example, it can be freely adjusted within the range of 0.01 μm or more and 1.000 μm or less. If the thickness of the polyimide-based resin film increases or decreases by a specific value, the physical properties measured in the polyimide-based resin film may also change by a certain value.

The bow of the polyimide-based resin film may be 40 μm or less, or 35 μm or less, or 32 μm or less, or 0.1 μm or more and 40 μm or less, or 0.1 μm or more and 35 μm or less, or 0.1 μm or more and 32 μm or less, or 25 μm or more and 40 μm or less, or 25 μm or more 35 μm or less, or 25 μm or more and 32 μm or less.

The bow is also referred to as warpage or bow, which is a type of surface flatness properties of a material, and more specifically, for example, as a specific measuring method or the like, various methods widely known in the semiconductor wafer substrate manufacturing field can be applied without limitation.

Specifically, the bow 4 can be defined as a distance in a central axis between a thickness central plane 1 and a reference plane 2 (best fit plane of thickness central plane), as shown in FIG. 1.

The thickness center plane 1 refers to a plane connecting a point that is half (t/2) of the thickness t in the measurement object as shown in FIG. 1.

The reference plane 2 means a cross section by a straight line connecting the thickness center point at both ends of the measurement object, as shown in FIG. 1 below.

The central axis 3 refers to a straight line perpendicular to the horizontal plane passing through the center of gravity of the measurement object as shown in FIG. 1. As an example of a method of measuring the bow 4, a laser stress analyzer can be used, and the laser stress analyzer can automatically calculate and obtain a bow value by measuring the intensity of the light reflected from the back of the measurement sample and mathematically analyzing it.

The bow may be that which is measured for the polyimide-based resin film sample of the above-mentioned one embodiment having a thickness of 5 μm or more and 30 μm or less, or 5 μm or more and 15 μm or less, or 8 μm or more and 12 μm or less.

The polyimide-based resin film sample used for the measurement of the bow may include a pure polyimide-based resin film; or a laminate including a substrate film and a polyimide-based resin film coated on the substrate film. Examples of the substrate film are not particularly limited, and a glass substrate, a wafer substrate, or a mixture thereof may be used without limitation.

When the polyimide-based resin film sample used for the measurement of the bow is composed of only a pure polyimide-based resin film, the bow can be automatically measured through the results of analyzing a polyimide-based resin film sample by a laser stress analyzer. For example, a pure polyimide-based resin film can be secured through the process of peeling a substrate film from a laminate including the substrate film and the polyimide-based resin film coated on the substrate film.

Meanwhile, when the polyimide-based resin film sample is a laminate including a substrate film and a polyimide-based resin film coated on the substrate film, the bow of the pure polyimide-based resin film can be obtained through the value obtained by subtracting a bow of the substrate film from a bow of the laminate including the substrate film and the polyimide-based resin film coated on the substrate film, as shown in the following Equation 2.

Bow=(Bow of the laminate including a substrate film and a polyimide-based resin film coated on the substrate film)−(Bow of the substrate film)  [Equation 2]

Even if a pure polyimide-based resin film is used as the polyimide resin film sample used for the measurement of the bow, or a laminate including a substrate film and a polyimide resin film coated on the substrate film is used, the bow value of only the resulting polyimide-based resin film can exhibit an equivalent level value without error.

The lower the bow of the polyimide-based resin film means that the film has a flat surface, and as described above, the polyimide-based resin film of the embodiment may include a cured product of the polyimide-based resin cured at a temperature of 400° C. or more. The cured product is manufactured by curing the resin composition containing the polyimide-based resin at a temperature of 400° C. or more, or 400° C. or more and 500° C. or less for 20 minutes or more and 100 minutes or less. Thus, when the bow of the polyimide-based resin film is reduced to 40 μm or less, and when the polyimide-based resin film is applied to a substrate material for a display device described later, a stable flatness, is maintained even in a high temperature process and thus high reliability can be ensured.

In particular, in the polyimide-based resin film, a bow variation of the polyimide-based resin film obtained by the following Equation 1 may be 5 μm or less, or 3 μm or less, or 2.8 μm or less, or 0.01 μm or more and 5 μm or less, or 0.01 or more and 3 μm or less, or 0.01 μm or more and 2.8 μm or less.

Bow Variation (μm)=Bow_(f)−Bow  [Equation 1]

in Equation 1, Bow_(f) is the final bow value of the film obtained after further heat-treating the polyimide-based resin film at a temperature of 400° C. to 450° C.: for 50 minutes to 200 minutes, and Bow is the bow value of the polyimide-based resin film.

In the Bow_(f) of Equation 1, examples of the method of further heat treating the polyimide-based resin film at a temperature of 400° C. to 450° C. for 50 minutes to 200 minutes are not particularly limited. The heat treatment can be performed in a single stage or can be performed in a multi-stage. In the case of the multi-stage, it can pass through additional heat treatment in the second to tenth stage, and in this case, each step can be performed continuously or discontinuously.

However, if the heat treatment is performed sequentially, each heat treatment step is performed at a temperature of 400° C. to 450° C., and the total time of each heat treatment step satisfies 50 to 200 minutes.

As described above, when the polyimide-based resin film sample used for measuring the how variation of the polyimide-based resin film obtained by Equation 1 is an optical laminate including a substrate film and a polyimide-based resin film orated on the substrate film, the Bow_(f) of Equation 1 can be Obtained through Equation 3 below.

Bow_(f)=(Bow of the laminate including the substrate film and the polyimide-based resin film coated on the substrate film after additional heat treatment)−(Bow of the substrate film)  [Equation 3]

That is, despite the addition of the heat treatment conditions at a high temperature of 400° C. or more for the polyimide-based resin film of the one embodiment, the bow variation which is the surface flatness property of the film is 5 μm or less which very low, and thus, the polyimide-based resin film of the above one embodiment may realize high heat resistance.

2. Substrate for Display Device

Meanwhile, according to another embodiment of the present disclosure, there can be provided a substrate for display device including the polyimide-based resin film of the other embodiment. Details of the polyimide-based resin film may include all of the contents described above in the one embodiment.

The display device including the substrate may include a liquid crystal display device (LCD), an organic light emitting diode (OLED), a flexible display), a rollable display or foldable display, or the like.

The display device may have various structures according to an application field and a specific shape, and may include, for example, a cover plastic window, a touch panel, a polarizing plate, a barrier film, a light emitting device (such as an OLED device), a transparent substrate, or the like.

The polyimide-based resin film of another embodiment described above may be used in various applications such as a substrate, an outer protective film or a cover window in such various display devices, and more specifically, may be applied to a substrate.

For example, the display device substrate may have a structure in which a device protective layer, a transparent electrode layer, a silicon oxide layer, a polyimide-based resin film, a silicon oxide layer, and a hard coating layer are sequentially stacked.

The transparent polyimide substrate may further include a silicon oxide layer formed between the transparent polyimide-based resin film and the cured layer in order to further improve the solvent resistance, water permeability and optical properties thereof, and the silicon oxide layer may be produced by curing polysilazane.

Specifically, the silicon oxide layer may, before forming a coating layer on at least one surface of the transparent polyimide-based resin film, be formed by curing the coated polysilazane after coating and drying a solution containing polysilazane

The substrate for a display device according to the present disclosure can provide a transparent polyimide cover substrate having solvent resistance, optical properties, water permeability and scratch resistance while having excellent bow properties and impact resistance by including the above-described device protective layer.

3. Optical Device

Meanwhile, according to another embodiment of the present disclosure, there can be provided an optical device including the polyimide-based resin film of the other embodiment. Details of the polyimide-based resin film may include all of those described above in the one embodiment.

The optical device may include all kinds of devices using properties realized by light, and may be, for example, a display device. Specific examples of the display device include a liquid crystal display device (LCD), an organic light emitting diode (OLED), a flexible display, a rollable display or foldable display device, or the like, but is not limited thereto.

The optical device may have various structures according to the application field and the specific shape, and for example, it may have a structure including a cover plastic window, a touch panel, a polarizing plate, a barrier film, a light emitting device (such as an OLED device), a transparent substrate, or the like.

The polyimide-based resin film of another embodiment described above may be used in various applications such as a substrate, an outer protective film or a cover window in various optical devices, and more specifically, may be applied to a substrate.

Advantageous Effects

According to the present disclosure, a polyimide-based resin film capable of ensuring excellent flatness even under high temperature heat treatment conditions, and stably maintaining flatness even during further heat treatment, a substrate for display device, and an optical device using the same can be provided.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows a cross-sectional view of measuring the bow of Experimental Example 1 and Experimental Example 2.

Hereinafter, embodiments of the present disclosure will be described in more detail by way of examples. However, these examples are provided for illustrative purposes only, and are not intended to limit the scope of the present disclosure.

EXAMPLE: PREPARATION OF POLYIMIDE FILM Example 1

(1) Preparation of Polyimide Precursor Composition

The organic solvent. DEAc was filled in a reactor under a stream of nitrogen, and then 0.735 mol of a diamine represented by the following Chemical Formula a was added and dissolved at the same temperature while maintaining the temperature of the reactor to 25° C. To the solution to which the diamine represented by the following Chemical Formula a was added, 0.3675 mol of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF) represented by Chemical Formula b and 0.3675 mol of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) were added as an acid dianhydride at the same temperature, and stirred for 24 hours to give a polyimide precursor composition.

(2) Preparation of Polyimide Film

The polyimide precursor composition was spin coated on a glass substrate. The polyimide precursor composition-coated glass substrate was put in an oven and heated at a rate of 5° C./min, and a curing process was performed by maintaining at 80° C. for 20 minutes and at 450° C. for 70 minutes, thereby preparing a polyimide film (thickness: 10 μm).

Example 2

A polyimide film was prepared in the same manner as in Example 1, except that 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA) was used as acid dianhydride instead of 3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA).

Example 3

A polyimide film was prepared in the same manner as in Example 1, except that pyromellitic dianhydride (PMDA) was used as acid dianhydride instead of 3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA).

COMPARATIVE EXAMPLE: PREPARATION OF POLYIMIDE FILM Comparative Example 1

(1) Preparation of Polyimide Precursor Composition

The organic solvent. DEAc was filled in a reactor under a stream of nitrogen, and then 0.735 mol of 2,2′-bis(trifluoromethyl)benzidine (TFMB) was added and dissolved at the same temperature while maintaining the temperature of the reactor to 25° C. To the solution to which 2,2′-bis(trifluoromethyl)benzidine (TFMB) was added, 0.735 mol of 3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA) was added as an acid dianhydride at the same temperature, and stirred for 24 hours to give a polyimide precursor composition.

(2) Preparation of Polyimide Film

The polyimide precursor composition was spin coated on a glass substrate. The polyimide precursor composition-coated glass substrate was put in an oven and heated at a rate of 5° C./min, and a curing process was performed by maintaining at 80° C. for 20 minutes and at 450° C. for 70 minutes, thereby preparing a polyimide film (thickness: 10 μm).

Comparative Example 2

A polyimide film was prepared in the same manner as in Comparative Example 1, except that 0.3675 mol of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 0.3675 mol of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA) were added as an acid dianhydride.

Experimental Example: Measurement of Physical Properties of Polyimide Films Obtained in Examples and Comparative Examples

The physical properties of the polyimide films obtained in Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

1. Bow (Warpage)

The bow value of the polyimide film laminate (glass substrate+polyimide film) coated on a glass substrate obtained in each of Examples and Comparative Examples, and the bow value of only the glass substrate were measured, and the bow of the polyimide film was calculated according to the following Equation and described in Table 1 below.

Bow of Polyimide Film=(Bow of the polyimide film laminate coated on the glass substrate)−(Bow of the substrate only)  [Equation]

The bow is defined as a distance in a central axis between a thickness central plane and a reference plane (best fit plane of thickness central plane) as shown in FIG. 1, and the measurement of the bow was performed on a sample at room temperature using a stress analyzes (TENCOR FLX-2320).

2. Heat Resistant Bow (ΔBow)

(1) Additional Condition for Two High-Temperature Heat Curing (450° 070 Min→410° C./60 Min→445° C./60 Min Curing)

The bow value was measured after further curing the polyimide film laminate. (glass substrate+polyimide film) coated on the glass substrate obtained in each of Examples and Comparative Examples at 410° C. for 60 minutes, followed further curing at 445° C. for 60 minutes, and the bow value of only the glass substrate was measured, and the final bow (Bow_(f)) of the polyimide film was obtained according to the following Equation. Using this, the bow variation (ΔBow) of the polyimide film was calculated according to the following Equation, and described as heat-resistant bow (ΔBow) in Table 1 below. The measurement method of the how is the same as described in Experimental Example 1.

(2) Additional Conditions for Four High Temperature Heat Curing (450° C./70 Min→445° C./20 Min→445° C./20 Min→410° C./60 Min)

The bow value was measured after further curing the polyimide film laminate (glass substrate+polyimide film) coated on the glass substrate obtained in each of Examples and Comparative Examples at 445° C. for 20 minutes, followed by further curing at 410° C. for 60 minutes, and the bow value of only the glass substrate was measured, and the final bow (Bow_(f)) of the polyimide film was determined according to the following Equation. Using this, the bow variation (ΔBow) of the polyimide film was calculated according to the following Equation, and described as heat-resistant bow (ΔBow) in Table 1 below. The measurement method of the bow is the same as described in Experimental Example 1.

(3) Additional Conditions for Four High Temperature Heat Curing (450° C./70 Min→445° C./20 Min→445° C./20 Min→410° C./60 Min→445° C./60 Min Curing)

The bow value was measured after further curing the polyimide film laminate (glass substrate+polyimide film) coated on the glass substrate obtained in each of Examples and Comparative Examples at 445° C. for 20 minutes, followed further curing at 445° C. for 20 minutes, then further curing 410° C. for 60 minutes, and then further curing 445° C. for 60 minutes, and the bow value of only the glass substrate was measured, and the final bow (Bow_(f)) of the polyimide film was determined according to the following Equation. Using this, the bow variation (ΔBow) of the polyimide film was calculated according to the following Equation, and described as heat-resistant bow (ΔBow) in Table 1 below. The measurement method of the bow is the same as described in Experimental Example L

Final bow of polyimide film(Bow_(f))=(Bow of the polyimide film laminate coated on the glass substrate after additional heat treatment)−(Bow of the glass substrate)  [Equation]

Bow variation of polyimide film (ΔBow)=(Final bow of the polyimide film obtained in Experimental Example 2 (Bow_(f)))−(Bow of the polyimide film obtained in Experimental Example 1)  [Equation]

TABLE 1 Experimental Example Measurement Results of Examples and Comparative Examples Heat-resistant bow (ΔBow) Category 450° C./70 min → High 445° C./20 min → temperature Bow 450° C./70 min → 450° C./70 min → 445° C./20 min → curing 450° C./ 410° C./60 min → 445° C./20 min → 410° C./60 min → condition 70 min 445° C./60 min 410° C./60 min 445° C./60 min Example 1 30.2 μm 0.1 μm 0.4 μm 1.9 μm Example 2 31.5 μm 0.3 μm 0.6 μm 2.6 μm Example 3 28.9 μm 0.1 μm 0.3 μm 1.4 μm Comparative 56.4 μm 5.6 μm 8.4 μm 11.8 μm  Example 1 Comparative 72.6 μm 9.2 μm 16.3 μm  19.1 μm  Example 2

As shown in Table 1 above, the polyimide-based resin films of Examples 1 to 3 obtained through a curing process at 450° C. for 70 minutes showed a bow of 28.9 μm or more and 31.5 μm or less. Meanwhile, the polyimide-based resin films of Comparative Examples 1 and 2 obtained through a curing process at 450° C. for 70 minutes showed a bow of 56.4 μm or more and 72.6 μm or less, which is much higher than that of Examples.

Through this, it was confirmed that the polyimide-based resin films of Examples could have excellent flatness even during high temperature curing at 400° C. or more.

In addition, the polyimide-based resin films of Examples 1 to 3 showed a heat resistant bow (ΔBow) of 0.1 μm or more and 2.6 μm or less even when further heat treatment was performed at a high temperature of 400° C. or more.

On the other hand, when additional heat treatment was performed at a high temperature of 400° C. or more, the polyimide-based resin film of Comparative Examples 1 and 2 showed a heat resistant bow (ΔBow) of 5.6 μm or more and 19.1 μm or less, which was much higher than that of Examples.

Through this, it was confirmed that the polyimide-based resin films of Examples stably maintained the flatness even during high temperature heat treatment of 400° C. or more.

DESCRIPTION OF SYMBOLS

-   -   1: thickness central plane     -   2: reference plane (Best fit plane of thickness central plane)     -   3: central axis     -   4: bow 

1. A polyimide-based resin film comprising a polyimide-based resin containing a polyimide repeating unit represented by the following Chemical Formula 1, wherein Bow is 40 μm or less:

in the Chemical Formula 1, X₁ is a tetravalent functional group represented by the following Chemical Formula 2, Y₁ is an aromatic divalent functional group having at least 15 carbon atoms in which at least one electron-withdrawing group is substituted,

in the Chemical Formula 2, Ar is a polycyclic aromatic divalent functional group.
 2. The polyimide-based resin film of claim 1, wherein a Bow variation of the polyimide-based resin film obtained by the following Equation 1 is 5 μm or less: Bow Variation (μm)=Bow_(f)−Bow  [Equation 1] in the Equation 1, Bow_(f) is a final Bow value of the film measured after further heat-treatment of the polyimide-based resin film at a temperature of 400° C. to 450° C. for 50 minutes to 200 minutes, and Bow is the Bow value of the polyimide-based resin film.
 3. The polyimide-based resin film of claim 1, wherein the Bow is defined as a distance in a central axis between a thickness central plane and a reference plane of the polyimide-based resin film.
 4. The polyimide-based resin film of claim 1, wherein the Bow is measured for the polyimide-based resin film having a thickness of 5 μm or more and 30 μm or less.
 5. The polyimide-based resin film of claim 1, wherein the Bow is determined according to the following Equation
 2. Bow=(Bow of the laminate including a substrate film and a polyimide-based resin film coated on the substrate film)−(Bow of the substrate film)  [Equation 2]
 6. The polyimide-based resin film of claim 1, wherein the polycyclic aromatic divalent functional group of Ar of the Chemical Formula 2 includes a fused cyclic divalent functional group containing at least two aromatic cyclic compounds.
 7. The polyimide-based resin film of claim 1, wherein the polycyclic aromatic divalent functional group of Ar of the Chemical Formula 2 includes a fluorenylene group.
 8. The polyimide-based resin film of claim 1, wherein the tetravalent functional group represented by Chemical Formula 2 includes a functional group represented by the following Chemical Formula 2-1:


9. The polyimide-based resin film of claim 1, wherein the aromatic divalent functional group having at least 15 carbon atoms of Y₁ includes at least three aromatic cyclic compounds.
 10. The polyimide-based resin film of claim 9, wherein the aromatic divalent functional group having at least 15 carbon atoms includes at least one group selected from a triphenylene group, a quarterphenylene group, and a pentaphenylene group.
 11. The polyimide-based resin film of claim 1, wherein the electron-withdrawing group includes at least one group selected from a haloalkyl group, a halogen group, a cyano group, a nitro group, a sulfonic acid group, a carbonyl group, and a sulfonyl group.
 12. The polyimide-based resin film of claim 1, wherein the aromatic divalent functional group having at least 15 carbon atoms of Y₁ includes a functional group represented by the following Chemical Formula 3:

in the Chemical Formula 3, T₁ to T₃ are the same as or different from each other, and each independently, an electron-withdrawing group, m1 to m3 are the same as or different from each other, at least one of m1 to m3 is an integer of 1 to 4, the rest are an integer of 0 to 4, and n is an integer of 1 to
 10. 13. The polyimide-based resin film of claim 1, wherein the aromatic divalent functional group having at least 15 carbon atoms of Y₁ includes a functional group represented by the following Chemical Formula 3-1:


14. The polyimide-based resin film of claim 1, wherein the polyimide-based resin includes a combination of a tetracarboxylic dianhydride represented by the following Chemical Formula 4 and an aromatic diamine having or more carbon atoms in which at least one electron withdrawing group is substituted:

in the Chemical Formula 4, Ar′ is a polycyclic aromatic divalent functional group.
 15. The polyimide-based resin film of claim 1, wherein the polyimide-based resin further includes a polyimide repeating unit represented by the following Chemical; Formula 5:

in the Chemical Formula 5, X₂ is one of tetravalent functional groups represented by the following Chemical Formula 6, and Y₂ is an aromatic divalent functional group having at least 15 carbon atoms in which at least one of electron-withdrawing groups is substituted,

in the Chemical Formula 6, R₁ to R₆ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, L is any one selected from the group consisting of a single bond, —O—, —CO—, —COO—, —S—, —SO—, —SO₂—, —CR₇R₈—, —(CH₂)_(t)—, —O(CH₂)_(t)O—, —COO(CH₂)_(t)OCO—, —CONH—, phenylene or a combination thereof, where R₇ and R₈ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms, and t is an integer from 1 to
 10. 16. The polyimide-based resin film of claim 15, wherein the polyimide repeating unit represented by Chemical Formula 5 and the polyimide repeating unit represented by Chemical Formula 1 are contained in an amount of 70 mol % or more with respect to the total repeating units contained in the polyimide-based resin.
 17. The polyimide-based resin film of claim 1, wherein the polyimide-based resin film includes a cured product in which the polyimide-based resin is cured at a temperature of 400° C. or more.
 18. A substrate for display device comprising the polyimide-based resin film of claim
 1. 19. An optical device comprising the polyimide-based resin film of claim
 1. 